nanomaterials
Article
Construction and Mechanism Analysis of a Self-Assembled
Conductive Network in DGEBA/PEI/HRGO Nanocomposites
by Controlling Filler Selective Localization
Yiming Meng 1,2 , Sushant Sharma 1 , Wenjun Gan 2 , Seung Hyun Hur 1 , Won Mook Choi 1
Jin Suk Chung 1, *






Citation: Meng, Y.; Sharma, S.; Gan,
W.; Hur, S.H.; Choi, W.M.; Chung, J.S.
Construction and Mechanism
Analysis of a Self-Assembled
Conductive Network in DGEBA/
PEI/HRGO Nanocomposites by
Controlling Filler Selective
Localization. Nanomaterials 2021, 11,
228. https://doi.org/10.3390/
nano11010228
Received: 24 December 2020
Accepted: 11 January 2021
Published: 16 January 2021
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Copyright: © 2021 by the authors. Li-
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4.0/).
Nanomaterials 2021, 11, 228. https://doi.org/10.3390/nano11010228
and
1 School of Chemical Engineering, University of Ulsan, Daehakro 93, Namgu, Ulsan 44610, Korea;
mengyiming1112@gmail.com (Y.M.); sushant.nplindia@gmail.com (S.S.); shhur@mail.ulsan.ac.kr (S.H.H.);
wmchoi98@ulsan.ac.kr (W.M.C.)
2 Department of Macromolecular Materials and Engineering, College of Chemistry and Chemical Engineering,
Shanghai University of Engineering Science, Shanghai 201620, China; wjgan@sues.edu.cn
* Correspondence: jschung@mail.ulsan.ac.kr; Tel.: +82-052-259-2249
Abstract: Herein, a feasible and effective approach is developed to build an electrically conductive
and double percolation network-like structure via the incorporation of highly reduced graphene ox-
ide (HRGO) into a polymer blend of diglycidyl ether of bisphenol A/polyetherimide (DGEBA/PEI).
With the assistance of the curing reaction-induced phase separation (CRIPS) technique, an intercon-
nected network of HRGO is formed in the phase-separated structure of the DGEBA/PEI polymer
blend due to selective localization behavior. In this study, HRGO was prepared from a unique
chemical reduction technique. The DGEBA/PEI/HRGO nanocomposite was analyzed in terms
of phase structure by content of PEI and low weight fractions of HRGO (0.5 wt.%). The HRGO
delivered a high electrical conductivity in DGEBA/PEI polyblends, wherein the value increased
from 5.03 × 10−16 S/m to 5.88 S/m at a low content of HRGO (0.5 wt.%). Furthermore, the HRGO
accelerated the curing reaction process of CRIPS due to its amino group. Finally, dynamic mechanical
analyses (DMA) were performed to understand the CRIPS phenomenon and selective localization of
HRGO reinforcement. The storage modulus increased monotonically from 1536 MPa to 1660 MPa for
the 25 phr (parts per hundred in the DGEBA) PEI polyblend and reached 1915 MPa with 0.5 wt.%
HRGO reinforcement. These simultaneous improvements in electrical conductivity and dynamic
mechanical properties clearly demonstrate the potential of this conductive polyblend for various
engineering applications.
Keywords: polyblend; nanocomposites; reduced graphene oxide; curing reaction-induced phase
separation (CRIPS); selective localization; microstructural analysis
1. Introduction
In the 21st century, considering the global environment, energy efficiency and renew-
able energy technologies, the core elements for many such fields are polymer reinforced
composites and their derived products. With the rapid growth in development and us-
age of electronic and electrical equipment, electronic packaging of polymers has become
critical. Therefore, need for affordable multi-functional polymer materials has increased
significantly.
Epoxies are highly cross-linked thermosetting polymers. One common epoxy is
diglycidyl ether of bisphenol A (DGEBA), which possesses excellent corrosion resistance,
outstanding adhesion strength, low curing shrinkage, and excellent mechanical properties.
DGEBA is durable in harsh environments and dimensionally stable. Hence, it is widely
used in coatings [1,2], adhesives [3], supporting structural materials [4], automotive elec-
tron devices [5], and Electromagnetic interference shielding [6], several other engineering
https://www.mdpi.com/journal/nanomaterials
Nanomaterials 2021, 11, 228 2 of 18

applications [7,8]. However, this kind of structure has a few drawbacks that lead to brittle
failure, low impact resistance, and poor conductivity, which limit extensive use of DGEBA
epoxy resin in various engineering applications. To enhance the properties of the pristine
epoxy resin, researchers generally blend it with thermoplastic polymers [9], rubber [10],
or polysiloxane [11] as a modifier that can enhance energy dissipation mechanisms in
the matrix. These modifications result in appreciable improvement in the toughness of
the epoxy resin. However, this often causes a significant decrease in epoxy resin tensile
strength, modulus, and maximum performance temperature by lowering the glass tran-
sition temperature (Tg ) and does not contribute to electrical conductivity [12]. Higher
energy absorption at a maximum working temperature along with electrical conductivity
are important for a broad range of engineering applications.
Therefore, many nanofillers such as carbon nanotubes [13], graphene and deriva-
tives [14], carbides [15], nitrides [16], and hybrids [17–19] have been extensively used to
introduce electrical properties in polymers due to their inherited electrical conductivity and
high aspect ratios [20,21]. Several parameters affect the electrical conductivity of polymer
nanocomposites, such as interfacial resistance between filler and matrix, size and type of
filler, processing conditions, and localization of filler in the matrix system. It is quite chal-
lenging to maintain a well distributed network of nanofillers in a polymer matrix, which
is necessary for improving electrical conductivity. Generally, these nanofillers experience
strong van der Waals forces at loadings of 1–5 wt.% reinforcement, which reduce their
dispersion. Various strategies have been adopted in recent years to establish a uniform
network of nanofillers in polymer composites, such as segregating the structures of polymer
nanocomposites by compression molding [22–24] and reinforcing macroscopic scaffolds
of nanofillers network in a polymer matrix [25–27]. However, these polymer composites
are not categorized as economical multi-functional as their processing involves multiple
time-consuming steps.
Another technique is selective localization of nanofillers in an immiscible polyblend with
a dispersed network using a curing reaction-induced phase separation technique [28–30].
Double percolation was initially observed by Sumita et al. [31] in carbon black (CB)-filled
immiscible polymer blends. Thereafter, the double percolation concept was extensively
applied in carbon-based materials such as graphene nanoplatelets (GNPs) [32], functional
graphene oxide, carbon nanotubes (CNTs) [33], and carbon fiber (CFs) [34]. Physical mixing
of polymer blends (polyblends) can be divided into the following methods [35]: (i) me-
chanical mixing in rubber mills or extruders, (ii) polymerization of one monomer in the
presence of another, (iii) evaporation or precipitation from a mixture of polymer solutions,
and (iv) coagulation of a mixture of polymer lattices. However, polymerization in the
presence of another polymer is an economical and easily controllable technique to form
a low-percolation conductive network of carbon nanofillers in a multiphase polyblend.
For example, Zhang et al. [36] formed a co-continuous network of epoxy (EP)/polyether
sulfone (PES)/multiwalled carbon nanotubes (MWCNTs) and selectively localized the
MWCNTs in an epoxy-rich area using reaction-induced phase separation and filler local-
ization. In the experimental study, it was found that after 20 wt.% of PES mechanical
properties of polyblend increases along with high glass transition temperature (Tg ). With
the selective localization of MWCNTs network (4.8 wt.%) in polyblend, the electrical con-
ductivity increased by 450% compared to that without a PES polyblend. Luna et al. [37]
studied the effects of nanoparticles on the morphologies of various immiscible polyblends
and analyzed their effect of electrical properties of polyblend nanocomposites. The ana-
lytical study confirmed that reinforcement of nanofillers ensure a low thermal expansion
coefficient, high thermo-mechanical resistance, and superior electrical conductivity if the
blend exhibited a co-continuous microstructure in the fillers [38]. Huang et al. [28] used
the double percolation technique to control selective localization of CNTs. They prepared a
co-continuous immiscible polyblend of poly (lactic acid)/poly(ε-caprolactone) (PLA/PCL)
at a weight ratio of 50/50 and controlled the migration of MWCNTs from unfavorable
PLA to favorable PCL phase. As a result, percolation of PLA/PCL/MWCNT composites
Nanomaterials 2021, 11, 228 3 of 18

(0.97 wt.%) decreased by two orders of magnitude in PLA/MWCNT/PCL composites

(0.025 wt.%) for similar electrical conductivities. Hence, development of a conductive
composite is recommended with low conductive filler weight ratios and a combination
of dissimilar polyblends [39–41]. When the polyblend system contains a thermosetting
component, it is very difficult to control selective localization of conducting nanofillers at
the interphase. Generally, the fillers become concentrated in a particular phase depending
on the effect of the curing reaction on miscibility, which ultimately increases the percolation
threshold via dominance of a particular phase.
Hence, a facile approach was developed in this study to construct a conductive double
percolation network of highly reduced graphene oxide (HRGO) in a polyblend of diglycidyl
ether of bisphenol A/polyetherimide (DGEBA/PEI). In this technique, conductive HRGO
filler was introduced into DGEBA/PEI two-phase immiscible polyblend and was selec-
tively localized at the interphase or in the co-continuous phase. The DGEBA/PEI/HRGO
nanocomposite showed high electrical conductivity with a low concentration of nanofiller
(i.e., 0.5 wt.%) because of its double percolation structure. Furthermore, the structural and
morphological analyses of DGEBA/PEI/HRGO nanocomposites were conducted using a
field emission scanning electron microscope (FESEM) and an inverted optical microscope
(OM) to characterize the conductive network. The electrical conductivity of the nanocom-
posites was measured by using a four-point probe technique. The effects of HRGO on the
CRIPS behavior of the composites were analyzed by dynamic mechanical analysis (DMA),
and the influence of HRGO on the storage modulus and Tg of the DGEBA/PEI/HRGO was
analyzed in detail. This ergonomic approach and the ability to control the localization of a
nanofiller network are helpful in developing an economical multifunctional polyblend of
DGEBA/PEI/HRGO that can be used in various engineering applications such as electronic
coatings, packaging, and electromagnetic shielding.

2. Experimental Section
2.1. Materials
Commercial graphene oxide was supplied by Standard Graphene, Ulsan, Korea.
Diglycidyl ether of bisphenol A (DGEBA, DER 332) was provided by Dow Chemical
Co. ( Midland, MI, United States of America) with an epoxide equivalent weight of
171–175 g/eq. The curing agent methyl tetrahydrophthalic anhydride (Me-THPA) and
accelerator N, N-dimethylbenzylamine (DMBA) were obtained from Shanghai Reagent Co.,
China. Polyetherimide (PEI, Ultem@ 1000, Tg ≈ 217 ◦ C) was purchased from Goodfellow
Company (Huntingdon, United Kingdom). N, N-Dimethylformamide (DMF), ethanol
(EtOH), and methylene dichloride (CH2 Cl2 ) were purchased from Sigma-Aldrich (Louis,
MO, United States of America). All reagents were used without further purification.

2.2. Synthesis of Highly Reduced Graphene Oxide (HRGO)

The HRGO was prepared according to the method of Dang et al. [42], with some
adjustments. For this, 2000 mg graphene oxide (GO, Standard Graphene, Korea) was
added into a mixed solution of 800 mL N, N-dimethylformamide (DMF) and 200 mL
de-ionized water (DIW). The mixture was sonicated in an ultrasonic bath (Jeiotech UC-
10, 200 W, Seoul, Korea) for 3 h to form a homogenous suspension of GO (2 mg/mL).
Hydrazine reduction was achieved by adding 5 mL of hydrazine monohydrate (98%)
per 100 mL of GO suspension and stirring at 60 ◦ C in an oil bath for 24 h. The HRGO
suspensions were filtered and washed with large amounts of ethanol to remove excess
hydrazine monohydrate. The HRGO filter cakes were re-dispersed in ethanol by sonication
for 3 h (the temperature of the sonication bath was maintained below 30 ◦ C).
To determine the dispersibility of HRGO in ethanol, 50 mL of HRGO suspension was
centrifuged at 3000 RPM for 15 min. Then, 20 mL of the upper supernatant was collected,
coagulated by adding a few drops of HCl (1 M), and filtered. The filter cakes were washed
with ethanol for three times, dried in vacuum at 100 ◦ C, and weighed to calculate the
dispersibility of the HRGO.
Nanomaterials 2021, 11, 228 4 of 18

2.3. Preparation of DGEBA/PEI/HRGO Composites

Composites with and without HRGO were prepared by using following process. First,
DGEBA, PEI, and HRGO were weighed according to the formulations in Table S1 and
DGEBA/PEI/HRGO composites were denoted by DPxH. Where D, P, x, and H were
representing the DGEBA, the PEI, PEI parts per hundred in the DGEBA (phr), and 0.5 wt.%
of HRGO, respectively. PEI was dissolved in methylene dichloride (CH2 Cl2 ) with strong
magnetic stirring and was introduced into the HRGO solution via magnetic stirring at room
temperature. After that, the DGEBA was added to the PEI/HRGO blends with high-speed
magnetic stirring at 80 ◦ C for 2 h to remove the solvent from the mixture. Then, the blends
of DGEBA/PEI/HRGO were placed in a vacuum oven at 120 ◦ C for 12 h to degas the
mixtures and to remove the solvents. The mixture of curing agent Me-THPA and accelerator
DMBA at 400:1 ratio by weight (C-A solution) was added into the vacuum-removed blends
and stirred at 550 RPM and 120 ◦ C. The homogeneous blend was achieved by mixing, and
the few air bubbles caused by these processes were removed through vacuum treatment at
120 ◦ C for 10 min. Finally, the polyblends were pre-curing at 150 ◦ C for 5 h and continued
by post-curing at 200 ◦ C for 2 h after pouring into the pre-prepared mold (Figure 1). The
residual samples in the beaker were stored in a refrigerator for OM measurement. For
comparison, neat DGEBA, DP5, DP10, DP15, DP20, DP25, and DP30 were prepared by the
same process.

2.4. Measurement and Characterization

Optical microscopy (OM) measurements were performed on an inverted metallurgical
microscope (DMI3000B, Leica, Seoul, Korea) to observe the phase separation behavior and
double percolation structure. Scanning electron microscope (SEM) (S-3400N, Hitachi High-
Technologies, Chicago, IL, United States of America) analyses were conducted to observe
the morphology of the HRGO. Transmission electron microscopy (TEM) measurements
were performed on a field emission transmission electron microscope (Tecnai G2 F20 X-
Twin, FEI Co., Hillsboro, OR, United State of America) operated at an acceleration voltage
of 200 kV. The ultrathin film (thickness:100–200 nm) composite samples were prepared at
room temperature using an ultramicrotome (RMC CR-X, Boeckeler Instruments, Tucson,
AZ, United States of America) equipped with a glass knife. The volume resistivity and
volume conductivity of nanocomposites were measured at room temperature using a four-
point probe technique with (CMT-100, AiT Co., Gyeonggi, Korea). Nanocomposites were
prepared in a disk shape (approximately 40 mm diameter and 2 mm thickness) for conduc-
tivity measurements (Figure 1). The thermomechanical properties of the nanocomposites
were performed by dynamic mechanical analysis (DMA) (TA Q800, TA instrument, New
Castle, DE, United States of America) in single cantilever mode at a frequency of 1 Hz and
oscillation strain of 0.2. The temperature ranges were 30–180 ◦ C and 30–230 ◦ C at a heating
rate of 3 ◦ C/min for the neat DGEBA and other nanocomposites, respectively. The samples
were cast in square aluminum molds, yielding a specimen geometry of 45 mm × 10 mm ×
3 mm (Figure 1). The contact angle (CA) measurements of DGEBA, PEI, and HRGO films
with various liquids were measured using a (Phoenix 300, SEO, Komachine Co., Seoul,
Korea). The CA measurements were conducted using the sessile drop method at room tem-
perature with 15–17 µL volume drops of liquids that were prepared with a micro syringe.
The surface tension and polarity of deionized water, glycerol, and formamide are shown
in Table S1. The Raman spectra were characterized using a confocal Raman microscope
(Thermo Scientific, Seoul, Korea) with a 532 nm wavelength monochromatic excitation
laser with 2 mW laser power and a 5 s exposure time. Furthermore, Fourier transform
infrared (FT-IR) spectra were recorded using (FT-IR, Thermo Electron Co., Waltham, MA,
United States of America). Differential scanning calorimeter (DSC) measurements were
performed by (TA Q20 V24.10, TA instrument, New Castle, DE, United States of America).
Nanomaterials 2021, 11, x FOR PEER REVIEW 5 of 19

Electron Co., Waltham, MA, United States of America). Differential scanning calorimeter
Nanomaterials 2021, 11, 228 5 of 18
(DSC) measurements were performed by (TA Q20 V24.10, TA instrument, New Castle,
United States of America).

illustration of
Figure 1. Schematic illustration of preparation
preparationof
ofDGEBA/PEI/HRGO
DGEBA/PEI/HRGO polyblend
polyblend nanocomposites
nanocomposites and the phase structure
process.
during the process.

3. Results and Discussion

3. Results and Discussion
3.1. Physical and Morphological Properties of HRGO
3.1. Physical and Morphological Properties of HRGO
A low-magnification SEM micrograph of an HRGO flake is shown in Figure 2a. GO
A low-magnification SEM micrograph of an HRGO flake is shown in Figure 2a. GO is
is a 2D sheet-like structure and contains multiple lamellar layers that open into a few lay-
a 2D sheet-like structure and contains multiple lamellar layers that open into a few layers
ers with improved graphitic structure after reduction. Figure 2a represents the opened
with improved graphitic structure after reduction. Figure 2a represents the opened flakes
flakes of graphene layers with irregular and folding which is caused due to acid treatment.
of graphene layers with irregular and folding which is caused due to acid treatment. They
They are entangled with each other and helpful in creating a dispersed network by selec-
are entangled with each other and helpful in creating a dispersed network by selective
tive localization
localization while
while reinforcing
reinforcing the polyblend.
the polyblend. Figure
Figure 2b shows
2b shows a TEM
a TEM image
image of single-
of single- or
or few-layer HRGO nanosheets with many wrinkles. These kinds of 2D
few-layer HRGO nanosheets with many wrinkles. These kinds of 2D wrinkled structures wrinkled struc-
tures are useful
are useful in improving
in improving the reinforcement
the reinforcement efficiency
efficiency of HRGO.of HRGO.
However, However,
it is veryitdifficult
is very
difficult
to predicttothepredict
actual the actual
changes in changes
structurein structure
after after
reduction reduction
from these SEMfrom
andthese
TEMSEM and
analyses.
TEM analyses. Therefore, Raman analysis was also conducted on
Therefore, Raman analysis was also conducted on these before reinforcement. these before reinforce-
ment.Raman spectroscopy provides information based on inelastic scattering of a molecule
irradiated by a monochromatic light, where laser is normally used. Figure 2c shows
Raman spectra for GO and HRGO, with two fundamental vibrations observed in the
range of 1100–1700cm−1 . The D vibration band (D-band) was observed at 1345.9 cm−1
and 1344.008 cm−1 for GO and HRGO, respectively. On the other hand, the G vibration
band (G-band) appeared at 1590.8 cm−1 and 1586.5 cm−1 for GO and HRGO, respectively.
Furthermore, the G vibration band is affected by the presence of the stretching C–C bond,
which is common in all sp2 carbon systems. The D band and G band in the Raman spectra
symbolize disorder bands and tangential bands, respectively. Besides, a broadening and
shift to higher wavenumbers of the 2D band were observed at 2684.2 cm−1 and 2673.6 cm−1
for GO and HRGO, respectively. The 2D band can be used to determine number of layers
Figure 2. (a) SEM micrograph of HRGO flakes
of graphene after drying,
(monolayer, double(b)layer,
TEM micrograph of HRGO
or multilayer) as it isand (c) Raman
highly spectra
sensitive of stacking
to the GO
and HRGO flakes. of graphene layers. In addition, the shifted location of the 2D band is due to the presence
of oxygen-containing functional groups and prevents graphene layer stacking of HRGO.
Thus, fewer oxygen-containing functional groups remained, allowing the RGO to stack.
The ID /IG ratio for GO was 0.847. After reduction, the ratio for HRGO increased to 1.063
due to restoration of sp2 carbon and decrease in the average size of sp2 domains upon
 3. Results and Discussion
3.1. Physical and Morphological Properties of HRGO
Nanomaterials 2021, 11, 228 A low-magnification SEM micrograph of an HRGO flake is shown in Figure 2a.6 of GO18
is a 2D sheet-like structure and contains multiple lamellar layers that open into a few lay-
ers with improved graphitic structure after reduction. Figure 2a represents the opened
flakes of graphene layers with irregular and folding which is caused due to acid treatment.
reduction
They [43,44]. The
are entangled withhigher intensity
each other and in the Dinband
helpful also asuggested
creating dispersedthat moreby
network isolated
selec-
graphene domains were present in HRGO compared to GO due to removal
tive localization while reinforcing the polyblend. Figure 2b shows a TEM image of single- of oxygen
moieties
or fromHRGO
few-layer GO after hydrazinewith
nanosheets reduction
many [45,46]. Further,
wrinkles. Theseto observe
kinds thewrinkled
of 2D reductionstruc-
state
of HRGO, FT-IR analysis was also conducted. Figure S1 represents the FT-IR spectra
tures are useful in improving the reinforcement efficiency of HRGO. However, it is very of GO
and HRGO, which confirms the reduction of GO after hydrazine treatment. After
difficult to predict the actual changes in structure after reduction from these SEM and reduction
of GO,
TEM a new amino
analyses. groupRaman
Therefore, from hydrazine
analysis was
was found in HRGO on
also conducted which helped
these accelerating
before reinforce-
the
ment.curing reaction process.

Figure 2. (a)
Figure 2. (a) SEM
SEM micrograph
micrograph of
of HRGO
HRGO flakes
flakes after
after drying,
drying, (b) TEM micrograph
(b) TEM micrograph of
of HRGO
HRGO and
and (c) Raman spectra
(c) Raman spectra of
of GO
GO
and HRGO flakes.
and HRGO flakes.

3.2. Morphology of DGEBA/PEI/HRGO as Observed by Optical Microcopy(OM) Measurement

Curing reaction-induced phase separation (CRIPS) is commonly described as sep-
aration of a homogeneous polyblend into two immiscible phases during curing. The
morphologies of the fabricated DGEBA/PEI/HRGO nanocomposites with different con-
tents of PEI were characterized by OM measurement (Figure 3). During the CRIPS process,
the polyblend followed a spinodal decomposition mechanism [47]. The DGEBA/PEI poly-
blend is a dynamic asymmetric system that initially is homogeneous. The molar mass of
the DGEBA increases as the isothermal curing reaction proceeds, resulting in an increase
in cross-linking density of DGEBA. Because large differences in mobility occur between
DGEBA molecular and PEI, the PEI is no longer miscible in the matrix, and PEI begins to
separate out, causing phase separation. The viscoelastic effect become more prominent
after primary phase separation, and this reduces the mobility of polymer chains of each
polymer as they diffuse into each other. When the diffusion is too slow to achieve geomet-
rical coarsening, the local concentration equilibrium is disrupted, and secondary phase
separation will occur in both DGEBA-rich and PEI-rich domains [48].
Figure 3a–g shows the final phase of the DGEBA/PEI/HRGO nanocomposites with
various PEI contents. The final phase structure changed from a Figure 3a-like insulated
island dispersed phase structure to a Figure 3e micro-size co-continuous phase structure,
with a PEI concentration from 5 to 25 phr of DGEBA, respectively. Furthermore, an
inversion phase structure (PEI-rich phase as matrix) appeared in the polyblend with
increased concentration of PEI, as depicted in Figure 3f.
The PEI-rich phase is represented as darker domains, and the DGEBA-rich phase as
brighter domains (Figure 3f). Further these separated phases were confirmed by FETEM
analyses in upcoming section. Occurrence of secondary phase separation, which shows
many small droplets in both domains at the final stage of phase separation, as in Figure 3e–g,
concur well with the state of viscoelastic phase separation reported by Tanaka et al. [49].
Nanomaterials 2021, 11, 228 7 of 18
Nanomaterials 2021, 11, x FOR PEER REVIEW 7 of 19

FigureFigure 3. The final phase morphologies of DGEBA/PEI/HRGO nanocomposites are (a) DP5H, (b) DP10H, (c) DP15H, (d)
3. The final phase morphologies of DGEBA/PEI/HRGO nanocomposites are (a) DP5H, (b) DP10H, (c) DP15H,
DP20H, (e) DP25H, (f) DP30H, and (g) DP30, respectively.
(d) DP20H, (e) DP25H, (f) DP30H, and (g) DP30, respectively.
The PEI-rich phase is represented as darker domains, and the DGEBA-rich phase as
Compared
brighter with
domains the non-HRGO-filled
(Figure polyblend
3f). further these separated in were
phases Figure 3g, introduction
confirmed by FETEM of the
HRGO (Figure 3f) both suppressed the extent of coarsening (i.e., the sizes
analyses in upcoming section. Occurrence of secondary phase separation, which of the DGEBA-
shows
rich phases became smaller) and accelerated the curing process due to interactions between
-NH2 functional groups on the HRGO and DGEBA oligomer [42]. HRGO served as a
crosslinking accelerator as a chemical crosslinking point.
 rich phases became smaller) and accelerated the curing process due to interactio
tween -NH2 functional groups on the HRGO and DGEBA oligomer [42]. HRGO serv
a crosslinking accelerator as a chemical crosslinking point.

3.3. Field Emission Transmission Electron Microscopy (FETEM) Analyses

Nanomaterials 2021, 11, 228 8 of 18
The distribution of HRGO in DGEBA/PEI polyblend system and the phase stru
of polyblend were analyzed by the FETEM technique as well. Figure 4 represen
FETEM micrographs of the DP25H and DP30H polyblends, in which dark and whi
3.3. Field Emission
mainsTransmission
representsElectron
PEI andMicroscopy (FETEM)
DGEBA phase, Analyses Figure 4a shows a co-conti
respectively.
The distribution of HRGO in in
phase morphology DGEBA/PEI polyblend
low magnification system
which and the phase
is consistent with thestructure
optical microg
of polyblend were analyzed
and Figure by thethe
4b shows FETEM technique
crumpled as well.
surfaces (with Figure 4 represents
some wrinkles) the of HR
of sheets
FETEM micrographs of the DP25H
the interphase (betweenand DP30H
DGEBA andpolyblends,
PEI phase).in which
It is implieddarkthatand
thewhite
HRGO sheets
domains represents PEI and
selectively DGEBAatphase,
localized respectively.
the interphase Figure 4a
in DP25H. shows
Then, theahigh-resolution
co-continuous transm
phase morphology in low magnification which is consistent with
electron microscopy (HRTEM) image of DP25H exhibits fringes the optical micrographs
from which the d-sp
and Figure 4b value
showsofthe the HRGO was calculated to be 0.376 nm as depictedofinHRGO
crumpled surfaces (with some wrinkles) of sheets Figureat4c. Figur
the interphase represents
(between DGEBA
a typicaland PEI inversion
phase phase). It structure
is impliedofthat the HRGO
DP30H sheets
polyblend werelower to h
from
selectively localized at the interphase
magnifications. in DP25H.
The secondary phaseThen, the high-resolution
separation structure showed transmission
in Figure 4e, inv
electron microscopy
many (HRTEM) imageislands
dark insulated of DP25H
(PEIexhibits fringes
phase) and from which
numerous the d-spacing
crumpled HRGO sheets d
value of the HRGO was calculated to be 0.376 nm as depicted
uted at the interphase that between DGEBA and PEI phase. in Figure 4c. Figure 4d–f
represents a typicalComparing
phase inversion structure of DP30H polyblend from lower to
Figure 4a with Figure 4d, we observe the formation of different higher
magnifications.structures
The secondary phase separation
by increasing the contentstructure
of PEI fromshowed
25 to in
30 Figure 4e, involved
phr. Meanwhile, the FETEM
many dark insulated islands (PEI phase) and numerous crumpled HRGO
ysis is cohort with the OM micrographs and represents localization sheets distributed
of HRGO at the
at the interphase thatbetween
phase betweenDGEBA
DGEBAand andPEI
PEIsuccessfully.
phase.

Figure 4. FETEM
Figuremicrographs of (a–c) DP25H
4. FETEM micrographs polyblend
of (a–c) DP25Hfrom lower from
polyblend to higher
lowermagnification with inset in
to higher magnification (c) represent
with
HRTEM micrograph of localized HRGO at the interphase of DGEBA and PEI, and (d–f) represents DP30H
inset in (c) represents HRTEM micrograph of localized HRGO at the interphase of DGEBA and PEI, polyblend wit
phase inversion.
and (d–f) represents DP30H polyblend with phase inversion.

Comparing Figure 4a with Figure 4d, we observe the formation of different phase
structures by increasing the content of PEI from 25 to 30 phr. Meanwhile, the FETEM
analysis is cohort with the OM micrographs and represents localization of HRGO at the
interphase between DGEBA and PEI successfully.

3.4. Electrical Properties of Nanocomposites

Morphologic analyses of DP25H and DP30H demonstrated the existence of a co-
continuous phase and an inversion phase, respectively. HRGO was selectively located
at the interphase between DGEBA and the PEI phase and formed a double-percolation
conductive network structure. This dispersed network in polyblend is useful in introducing
conductivity to a composite system. Figure 5a,b illustrates the effects of PEI content and
PEI/HRGO content on the in-plane conductivity of polyblend and HRGO-reinforced
polyblend composites, respectively. Figure 5b shows that the electrical conductivities
 3.4. Electrical Properties of Nanocomposites
Morphologic analyses of DP25H and DP30H demonstrated the existence of a co-con-
tinuous phase and an inversion phase, respectively. HRGO was selectively located at the
interphase between DGEBA and the PEI phase and formed a double-percolation conduc-
Nanomaterials 2021, 11, 228 tive network structure. This dispersed network in polyblend is useful in introducing con-
9 of 18
ductivity to a composite system. Figure 5a,b illustrates the effects of PEI content and
PEI/HRGO content on the in-plane conductivity of polyblend and HRGO-reinforced poly-
blend composites, respectively. Figure 5b shows that the electrical conductivities gradu-
gradually increased
ally increased bybyincreasing
increasingthe
the PEI
PEI content
content when
whenHRGOHRGOwas wasintroduced
introduced into the the
into
DGEBA/PEI polyblend system. On the other hand, there was little change in the electrical
DGEBA/PEI polyblend system. On the other hand, there was little change in the electrical
conductivity of polyblend
conductivity of polyblendwithout HRGO,
without as represented
HRGO, in Figure
as represented 5a. 5a.
in Figure

Figure 5. The
Figure electrical
5. The properties
electrical of samples
properties for various
of samples PEI contents:
for various (a) DGEBA/PEI,
PEI contents: (b) DGEBA/PEI/0.5
(a) DGEBA/PEI, wt.%
(b) DGEBA/PEI/0.5 HRGO.
wt.% HRGO.

However,
However,the the
phase morphologies
phase morphologiesof the
of nanocomposites, especially
the nanocomposites, phasephase
especially continuity,
continu-
play an important role in establishing a conductive network of filler in polymer composites.
ity, play an important role in establishing a conductive network of filler in polymer com-
Theposites.
volumeTheresistivity
volumeand conductivity
resistivity of DGEBA with
and conductivity similarwith
of DGEBA concentrations of PEI and of
similar concentrations
0.5 PEI
wt.% HRGO are presented in Figure 5b and Table 1. With HRGO reinforcement
and 0.5 wt.% HRGO are presented in Figure 5b and Table 1. With HRGO reinforce- in
DGEBA, the conductivity reached 1.83 S/m, and it increased with respect to
ment in DGEBA, the conductivity reached 1.83 S/m, and it increased with respect to PEIPEI concentra-
tion increases. In the DP25H, the conductivity reached ~5 S/m, an overall improvement
concentration increases. In the DP25H, the conductivity reached ~5 S/m, an overall im-
of 173% compared to that without PEI. After reaching 25 phr of PEI, the conductivity
provement of 173% compared to that without PEI. After reaching 25 phr of PEI, the con-
remained nearly constant, but an inversion phase structure affected the thermomechanical
ductivity remained nearly constant, but an inversion phase structure affected the thermo-
properties of the overall polyblend system. Furthermore, the comparison of electrical
mechanical properties of the overall polyblend system. Furthermore, the comparison of
properties with other previously reports are shown in Table 2.
electrical properties with other previously reports are shown in Table 2.
Table 1. The volume resistivity and volume conductivity of DGEBA/PEI polyblend with and
Table 1. The volume resistivity and volume conductivity of DGEBA/PEI polyblend with and with-
without HRGO.
out HRGO.
Materials Volume Resistivity
Materials Volume Resistivity (Ω cm) Conductivity
(Ω cm) Volume Volume Conductivity
(S/m) (S/m)
17 − 16
NeatNeat DGEBA
DGEBA 3.67 × 1017 3.67 × 10 2.67 × 10−162.67 × 10
DP0H DP0H 54.60 54.60 1.83 1.83
DP5H 31.06 3.22
DP5H 31.06 3.22
DP10H 28.23 3.54
DP10HDP15H 28.23 26.41 3.54 3.78
DP15HDP20H 26.41 24.11 3.78 4.15
DP20HDP25H 24.11 20.09 4.15 4.98
DP30H 17.02 5.88
DP25H 20.09 4.98
DP30H 17.02 5.88
The simultaneous blending of PEI with the curing reaction causes phase separation
due to a spinodal shift, allowing formation of a co-continuous network structure. This
network improves the dispersion state of HRGO and improves the conductivity. This
conducting property of nanocomposites is determined by selective localization of filler
particles in the polyblend. There are various thermodynamic strategies to control selective
localization of filler. The most widely used thermodynamic parameters for localization are
the wetting parameters, which are described in an upcoming section [36].
Nanomaterials 2021, 11, 228 10 of 18

Table 2. Comparison of volume resistivity and conductivity with those of previously published filler polyblend.

Volume Volume
Filler Loading
Samples Polymer A Polymer B Resistivity Conductivity [Ref]
(wt. %)
(Ω cm) (S/m)
EP/35PEI/GnPs DGEBA PEI 2 ≈107 ≈10−5 [50]
EP/PES/MWCNT DGEBA PES 4.8 — 10−1 [36]
EP/PEI/CB DGEBA PEI 1 ≈103 — [51]
DGEBA/PEI/MWCNTs DGEBA PEI 2 3.86 × 106 — [52]
9.6 × 105 Ω
DGEBA/PEI/AgNWs DGEBA PEI 3 (surface — [53]
resistivity)
EP/AIN/MWCNTs DGEBA AIN 6 — 10−10 [54]
EP/PA/MWCNT DGEBA PA 1 — 10−3 [55]
DGEBA/PEI/HRGO DGEBA PEI 0.5 1.7 × 101 5.88 This work

3.5. Prediction for Selective Localization of HRGO

Various studies of different complex parameters have been conducted for localiza-
tion of a filler in an immiscible polyblend. Accurate analysis of localization is difficult
because, in addition to thermodynamics, the fluid dynamics, surface tension, and polarity
of constituent blends during reaction are very important [56–61]. However, still wettability
parameter is a useful technique as it considers the surface tension of each component in the
blend. To precisely evaluate the surface tension of DGEBA, PEI, and HRGO, we conducted
contact angle measurements in conjunction with the Lifshitz–van der Waals/acid-base
approaches (Equations (1) and (2)) [56,57]. The values of these surface tension components
and parameters of the test liquids used in this work are shown in Table 3. Digital images
of the contact angles and values of three components are shown in the Supplementary
Materials (Figure S2 and Table S3).
q q q 
Lw Lw + − − +
γL (1 + cos θ) = 2 γs γL + γs · γL + γs · γL (1)

q
γAB
L =2 γL− · γL+ (2)

Table 3. Surface tension components and parameters (in mJ/m2 ) and static contact angles for the test
liquids DGEBA, PEI, and HEGO.

γL γL LW (γL d ) γL AB (γL P ) Contact Angle (θ)

Liquid
(mJ/m2 ) (mJ/m2 ) (mJ/m2 ) DGEBA PEI HRGO
Deionized water (DI) 72.8 21.8 51 88.4 84.2 80.5
Glycerol (GL) 64.0 34.0 30 84.3 75.0 55.0
Formamide (FA) 58.0 39.0 0 54.1 58.8 27.1

The Lifshitz–van der Waals/acid-base approaches proposed by Van Oss et al. [56,57]
combine dispersion (γd ), polar (γP ), and γi components into a single component, called the
nonpolar or Lifshitz–van der Waals component (γLW ). Also, the electron acceptor-electron
donor (Lewis acid/base) interactions of polar composites are expressed as γAB , and the
surface tension of compound i (L: liquid, S: solid) is expressed as γi + (acidic component)
γi − (basic component) according to Equation (2). Eventually, the total surface tension is
obtained by addition of the nonpolar and polar components (γtot = γLW + γAB ). Combining
this method with the Young-Dupré equation yields Equation (1).
Since Equation (1) contains three unknowns of the solid (γS LW , γS + , and γS − ), we
used three different liquids (in Table 3), two of which were polar. In our work, the surface
Nanomaterials 2021, 11, 228 11 of 18

tensions of DGEBA, PEI, and HRGO were calculated by Lifshitz–van der Waals approaches
as shown in Table 4.

Table 4. The surface tension components and parameters (in mJ/m2 ) obtained from the contact angle
data in Table 3 for the free surfaces of DGEBA, PEI, and HRGO.

Materials γ (mJ/m2 ) γd (mJ/m2 ) γP (mJ/m2 )

DGEBA 103.79 92.44 11.35
PEI 131.68 126.62 5.06
HRGO 93.99 93.67 0.32
HRGO: highly reduced graphene oxide; PEI: polyetherimide; γ = γd + γP .

The surface tension of each component in the polyblend is considered essential

for predicting the localization. From a thermodynamics perspective, the wetting coef-
ficient (ωa ) proposed by Sumita et al. [62] was widely used to forecast the localization of
nanofillers [51,63,64]. The wetting coefficient ωa can be calculated according to Young’s
equation (Equation (3)) as given below:

γHRGO−B − γHRGO−A
ωa = (3)
γA−B

where γHRGO-B is the interfacial tension between HRGO and the polymer B phase, γHRGO-A
is the interfacial tension between HRGO and the polymer A phase, and γA−B is the
interfacial tension between the polymer A phase and polymer B phase. The prediction is
that HRGO will be distributed preferentially in the polymer B phase if ωa < −1, HRGO
will be located at the interphase between polymer A and polymer B if −1 < ωa < 1 and
HRGO will be distributed in the polymer A phase if ωa > 1.
The interfacial tension between the two phases of nanocomposites, γA−B , can be
calculated using Wu’s harmonic mean average [65] as follow:
p
!
γdA γdB γPA γB
γA−B = γA + γB − 4 + P (4)
γdA + γdB γA + γPB

where γA−B is the interfacial tension between phases A and B. γA and γB are the surface
tensions of phases A and B, respectively. γd A and γd B are the surface tensions of disper-
sion components A and B, respectively. γp A and γp B are the surface tensions of polar
components A and B, respectively, for which γ = γd + γp .
In our DGEBA/PEI/HRGO polyblend system, the surface tensions of components are
shown in Table 4, and the interfacial tension and calculated wetting coefficient are given in
Table 5. From these calculations −1 < ωa = 0.171 < 1, indicating that the HRGO selectively
localizes at the interphase in DGEBA/PEI/HRGO systems. This prediction is consistent
with the OM images.

Table 5. The wetting coefficient (ωa ), interfacial tension (γpair ), and predicted localization of HRGO in DGEBA/PEI/HRGO polyblends.

γpair
Nanocomposites Phase A Phase B Component Pair ωa Predicted Localization of HRGO
(mN/m)
DGEBA/PEI 7.74
DGEBA/PEI/HRGO DGEBA PEI DGEBA/HRGO 10.42 −1 < 0.171 < 1 Interphase
PEI/HRGO 9.10

3.6. Mechanism of HRGO Localization

Considering the final electrical properties of the ternary nanocomposites, selective
localization of nanofiller in a polyblend is the key factor for controlling these properties.
Introducing the electrical conductivity with very low filler content is very important. In
creation of polyblend, crosslinking of DGEBA begins once the temperature increases to the
Nanomaterials 2021, 11, 228 12 of 18

curing temperature, and this is the starting point for phase separation [66,67]. As curing
continues, the spinodal downshift led to formation of a co-continuous phase structure.
The HRGO nanoparticles were uniformly mixed in the polyblend (Figure 6a). During
curing of DGEBA, an island-like structure is formed and progressively increases until the
dynamic forces between DGEBA and PEI are in balance. Here, HRGO nanoparticles due to
double percolation formed a conductive network at the interphase of DGBEA and PEI, as
represented in Figure 6a,b.
Figure 6b presents the TEM micrograph of DP25H nanocomposites in which the two
phases of DGEBA and PEI are represented by yellow and orange color dots, respectively.
The HRGO particles are clearly visible at the interphase of the two polymers, forming
a conductive network in the polyblend at a very low concentration. Table 2 compares
our work with previous literature, showing high electrical properties in comparison with
others work. Moreover, the content ratio of nanofiller HRGO in our work is very low (only
Nanomaterials 2021, 11, x FOR PEER REVIEW 13
0.5 wt.% of filler) for achieving the similar or more electrical conductivity compared to
others work.

Figure 6. Schematic
Figureillustration:
6. Schematic(a) structural evolution
illustration: of doubleevolution
(a) structural percolationofconductive DGEBA/PEI/HRGO
double percolation nanocom-
conductive
posites via CRIPS and (b) FETEM image of nanocomposite.
DGEBA/PEI/HRGO nanocomposites via CRIPS and (b) FETEM image of nanocomposite.

3.7. Dynamic3.7. DynamicAnalyses

Mechanical Mechanical Analyses (DMA)
(DMA)
Thebehavior
The viscoelastic viscoelastic behavior of HRGO-reinforced
of HRGO-reinforced polyblends and polyblends and selective
selective localization of localiza
of HRGOs in nanocomposites
HRGOs in nanocomposites have been studied have been
using studied
dynamic using dynamic
mechanical analysismechanical
(DMA). anal
(DMA).
DMA provides DMA provides
a sinusoidal a sinusoidal
load over load sample
the clamped over theand
clamped sample
compares and
this compares
with the this w
the collected response using a linear variable differential transformer (LVDT). Specifica
the LVDT measures the amplitude of the resulting sinusoidal wave, which is the stor
modulus (E’) of the material, and the tangent of the phase lag between applied force
material response (tan δ) [13].
Nanomaterials 2021, 11, 228 13 of 18

collected response using a linear variable differential transformer (LVDT). Specifically,

the LVDT measures the amplitude of the resulting sinusoidal wave, which is the storage
modulus (E’) of the material, and the tangent of the phase lag between applied force and
material response (tan δ) [13].
Figure 7a–d presents the storage modulus versus temperature curve of the DGEBA/PEI
polyblend with various phr of PEI and that of the DGEBA/PEI/HRGO nanocomposite
with various phr of PEI and a fixed concentration of HRGO (0.5 wt.%). Figure 7a presents
the storage modulus of a polyblend without HRGO. The storage modulus of neat DGEBA is
1536 MPa in the glassy region (measured at 30 ◦ C) and 14.2 in the rubbery region (measured
at Tg + 30 ◦ C). The storage modulus increased with PEI and reached maximum values of
1660 MPa and 68 MPa in the glassy and rubbery regions, respectively, for 25 phr PEI. The
storage modulus of DP25 was higher for the entire working temperature range (30–180 ◦ C),
which suggests that restriction of polymer chains in the polyblend is primarily due to
phase separation but also to arrested motion of the thermoplastic monomer chain between
DGEBA-rich zones. Figure 7b shows curves of the storage modulus in the temperature
range of 80–130 ◦ C, and it clearly indicates the restriction of polymer chain motion at
the beginning of the transition zone (glassy to rubbery). Ultimately, the immiscible poly-
mer blending resulted in a binary polymer system that is capable of withstanding higher
temperatures than that of DGEBA alone.
Figure 7c and Table 6 show the effect of reinforcement of HRGO on the thermomechan-
ical properties of DGEBA/PEI/HRGO nanocomposites with different phr fractions of PEI
and a fixed weight ratio of HRGO. The storage moduli of ternary polyblend nanocompos-
ites increased with increasing PEI concentration. The storage modulus of DP25H reached
1915 MPa and 64.8 MPa in the glassy and rubbery regions, respectively, and showed an
overall improvement of ~14% and ~222% over the baseline DGEBA nanocomposite (i.e.,
without polyblend DP0H). The HRGO reinforcement in polyblend played a crucial role
in improving the thermomechanical properties, as depicted in Figure 7d. Although the
storage modulus is high for the entire temperature range in DP25H, the effect is more
prominent at the beginning of transition (i.e., 80–130 ◦ C), where there was a significant
difference in the storage.
Tan δ versus temperature curves of DGEBA/PEI polyblend and DGEBA/PEI/HRGO
nanocomposites are given in Figure 8. The curves in Figure 8a–c demonstrate that the
glass transition temperature (Tg ) increased with blending concentration of PEI. The Tg
of base DGEBA was 123.1 ◦ C. After blending with PEI, it increased to 133.8 ◦ C for DP25,
an improvement of 10.7 degrees (Tg1 in Table 6). On the other hand, the Tg of neat PEI
was 217 ◦ C, which was reduced after blending with DGEBA (Tg2 in Table 6). The Tg2 of
the DP25 was 192 ◦ C. When HRGO was added to the polyblend, the Tg2 showed similar
results (Figure 8d–f). The Tg1 of DP25H reached 131.6 ◦ C, which is close to the Tg1 of DP25
but higher than that of DGEBA/0.5HRGO (123.3 ◦ C). The Tg2 of DP25H was 198.2 ◦ C,
higher than that of DP25 (192.0 ◦ C). This implies that addition of HRGO in the polyblend
restricts polymer chain motion of both DGEBA and PEI. However, it is more prominent
for PEI, as it exists only at the narrow zones between the large islands of DGEBA created
during phase separation. The decrease in peak height of tan δ in polyblend (Figure 8b)
and nanocomposite (Figure 8e) indicates the change in internal energy due to restriction
of molecular mobility caused by the increase in viscosity due to PEI and HRGO fillers,
respectively [68,69].
 reached 1915 MPa and 64.8 MPa in the glassy and rubbery regions, respectively, and
showed an overall improvement of ~14% and ~222% over the baseline DGEBA nanocom-
posite (i.e., without polyblend DP0H). The HRGO reinforcement in polyblend played a
crucial role in improving the thermomechanical properties, as depicted in
Nanomaterials 2021, 11, 228
Figure 7d. Although the storage modulus is high for the entire temperature range in
14 of 18
DP25H, the effect is more prominent at the beginning of transition (i.e., 80–130 °C), where
there was a significant difference in the storage.

Nanomaterials 2021, 11, x FOR PEER REVIEW 15 of 19

higher than that of DGEBA/0.5HRGO (123.3 °C). The Tg2 of DP25H was 198.2 °C, higher
than that of DP25 (192.0 °C). This implies that addition of HRGO in the polyblend restricts
polymer chain motion of both DGEBA and PEI. However, it is more prominent for PEI, as
it exists only at the narrow zones between the large islands of DGEBA created during
phase separation. The decrease in peak height of tan δ in polyblend (Figure 8b) and nano-
The storage
storage modulus
modulus versustemperature
temperature ◦ C and (b) a magnified view
Figure
Figure 7.
7. The composite
versus (Figure 8e)ofof DGEBA/PEI
indicates
DGEBA/PEI polyblend
thepolyblend
change in(a)(a)
atat
internal30–230
30–230energy
°C and due
(b) atomagnified
restriction of molec-
view of
of ◦
thethe beginning
beginning of transition
of the the transition
ular (80–130
(80–130 C). Storage
°C). caused
mobility Storage themodulus
modulus
by versus versus
increase temperature
temperature
in viscosity curves curves
due tofor andforHRGO
DGEBA/PEI/HRGO
DGEBA/PEI/HRGO
PEI nanocom-
fillers, respectively
posites with 0.5 wt.%
nanocomposites with HRGO
0.5 wt.%atHRGO
(c) 30–230 °C30–230
at (c) ◦ C80–130
and (d) 80–130 ◦ C.
°C.
and (d)
[68,69].

Tan δ versus temperature curves of DGEBA/PEI polyblend and DGEBA/PEI/HRGO

nanocomposites are given in Figure 8. The curves in Figure 8a–c demonstrate that the
glass transition temperature (Tg) increased with blending concentration of PEI. The Tg of
base DGEBA was 123.1 °C. After blending with PEI, it increased to 133.8 °C for DP25, an
improvement of 10.7 degrees (Tg1 in Table 6). On the other hand, the Tg of neat PEI was
217 °C, which was reduced after blending with DGEBA (Tg2 in Table 6). The Tg2 of the
DP25 was 192 °C. When HRGO was added to the polyblend, the Tg2 showed similar results
(Figure 8d–f). The Tg1 of DP25H reached 131.6 °C, which is close to the Tg1 of DP25 but

Figure 8. TanTan δδ versus

versustemperature
temperaturecurve
curvefor
forDGEBA/PEI
DGEBA/PEI polyblend:
polyblend: (a) 30–230◦°C,
(a) 30–230 100–150◦°C
(b)100–150
C, (b) forTTg1
C for 150–230 ◦°C
g1, (c) 150–230 C
g2,, and
for Tg2 and tan δ versus temperature
temperature curve
curvefor
forDGEBA/PEI/HRGO
DGEBA/PEI/HRGO nanocomposites: (d) 30–230 ◦
30–230 °C, 100–150 ◦°C
C, (e) 100–150 for TTg1
C for g1,

(f) 150–230
(f) 150–230 ◦°C for T
C for Tg2
g2..

Table 6. The storage modulus, rubbery modulus, and Tg (from tan δ) of samples.

Storage Modulus Rubbery Modulus Glass Transition Temperature (℃)

Materials
E’(MPa) ~~~(MPa) Tg1 Tg2
Neat DGEBA 1536 14.2 123.1
Nanomaterials 2021, 11, 228 15 of 18

Table 6. The storage modulus, rubbery modulus, and Tg (from tan δ) of samples.

Glass Transition Temperature (◦ C)

Materials Storage Modulus E’ (MPa) Rubbery Modulus (MPa)
Tg1 Tg2
Neat DGEBA 1536 14.2 123.1
DP5 1664 16.1 123.4 202.8
DP20 1687 38.8 128.8 194.1
DP25 1660 68.0 133.8 192.0
DP0H 1673 20.1 123.3
DP5H 1709 22.4 125.6 196.5
DP20H 1831 23.5 129.7 184.7
DP25H 1915 64.8 131.6 198.2
Neat PEI’s Tg : 217 ◦ C.

Further, to investigate the response of polyblends for heating, the DSC measure-
ments was also conducted. Figure S3 represents the DSC thermograms of DGEBA/PEI
and DGEBA/PEI/HRGO polyblends which confirms the HRGO accelerating the curing
reaction process.

4. Conclusions
In summary, we developed a three-dimensional double-percolation network of a
DGEBA/PEI/HRGO ternary system using a low content of 0.5 wt.% HRGO with the
assistance of CRIPS. The results confirmed our prediction that a unique ternary nanocom-
posite can be fabricated by controlling the location of the conductive filler HRGO at the
interphase. Furthermore, the electrical conductivity of polyblends increased by almost 16
orders of magnitude at a low content of 0.5 wt.% HRGO. The dynamic mechanical analyses
demonstrated that the storage modulus was continuously enhanced by increasing PEI
content and was enhanced by 15.4% with addition of 0.5 wt.% HRGO. The glass transition
temperature (Tg ) also increased with addition of PEI. Therefore, the DGEBA/PEI/HRGO
nanocomposites have significant potential for various engineering applications such as
electronic packaging, EMI shielding, electrostatic discharge, etc.

Supplementary Materials: The following are available online at https://www.mdpi.com/2079

-4991/11/1/228/s1, Figure S1: The FTIR spectra for HRGO and GO. Figure S2: The contact an-
gle images of samples. Figure S3: The DSC measurement of the DGEBA/PEI polyblends and
DGEBA/PEI/HRGO polyblends. Table S1: Formulation of samples. Table S2: Surface tensions and
components. Table S3: The static contact angles for the test liquids DGEBA, PEI, and HEGO.
Author Contributions: The research study was carried out in a collaboration of the aforementioned
authors and it was supervised by J.S.C.; Y.M. comprehended the idea and planned the experiments;
Y.M. wrote the manuscript, which was edited and reviewed by J.S.C., S.S., W.G., S.H.H. and W.M.C.
All authors have read and agreed to the published version of the manuscript.
Funding: This study was supported by the National Research Foundation of Korea (NRF) grant
funded by The Ministry of Science and ICT(MSIT)(2020R1A4A4079954).
Data Availability Statement: Data is contained within the article or Supplementary Materials.
Further, the published data can be reused by appropriate acknowledgement.
Conflicts of Interest: The authors declare no conflict of interest.

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